Polynitro diols



This invention relates to new and useful polynitro diols and to a method for their preparation. In particular, this invention is directed to polynitro diols having the general formula:

wherein A and A are lower alkylene radicals and R is a hydrogen or nitro radical The polynitro diols of our invention find valuable use as intermediatcsinthe preparation of high explosive compounds. They readily condense With the nitro isocyanate compounds such as 3,3,3-

tn'nitropropyl isocyanates, according to the method disclosed in assignees copending United States patent application Serial No. 479,656, filed January 3, 1956, now US. Patent No. 2,978,489, to form polynitro carbamate composition which are useful as high explosives. For extimple,i-i 4,4,6,8,8-pentanitro-l,1l-undecanediol condenses with 3,3,3-trinitropropyl isocyanate to form N,N'-bis(3,3, 3 trinitropropyl) 4,4,6,8,8-pentanitro-1,1l-undecanylene dica'rbamate. 'Thecompoundsthus prepared-are useful as high explosives and can beused in any conventional explosive missile, projectile, rocket, or the like, as the main explosive charge. An example of such a missile isrlisclosed: inUnited States Patent No. 2,470, 162,. issued May 17, 1949. One way of. using the high explosives in a device such as that disclosed in United States Patent No- 2,470,162 is to pack the crystalline explosive in powder form into the'warhead of the missile] Alternatively, the crystals can be first pelletized and then packed. A charge thus prepared is sufliciently insensitive to withstand the shock entailed in the ejection-of a-shell from a gun barrel or from a rocket launching tube under the pressure developed from ignition of a propellant charge, and can be caused to explode on operation of an impactor time-fuse mechanism firing a detonating explosive suchas lead azide or mercury fulminate.

It is well known that acyl halides may be reduced to theii" corresponding alcohols with reducing'ag'ents such as lithium aluminum hydride, and hydrogen in the pres ence of a catalyst. However, these conventional reducing agents all possess such strong reducing properties that the tothe cream-colored mixture.

3,000,965 Patented Sept. l9, 1 96 1 "ice wherein A and A are lower alkylene radicals, X is 'a halogen radical and R is a hydrogen or nitro radical.

The reduction is efiected by adding a solution of a nitroso zltaining acyl halide to a suspension of sodium borohy- Optimum results are obtained using a suspension of powdered sodium borohydride, about 200% excess, in an inert solvent such as dioxane.

1,4-dioxane is the preferred solvent due to its inert behavior and volatility. Any inert organic solvent can be used such as 2,4-dimethylsulfolane; however, dioxan'e is preferred since it can be separated from the product with greater ease. r

The compounds thus produced are obtained in a relatively pure form from the reaction mixture by hydrolyzing the sodium borohydride and its oxidation products in the aqueous phase, with a mineral acid, and recovering the product by crystallization, extraction or distillation from the nonraqueous phase.

The following examples are presented to more clearly illustrate our invention. These examples are presented purely as a means of illustration and do not in any way define either the limits or the scope of our invention; 0

EXAMPLE I Preparation of 4,4,6,8,8-pentanitf0-'1 ,1] -un'decaneciiol A reactor fitted with stirrer, dropping funnel and distillation apparatus, was charged with 8 gm. (6.75 gm; pure, 0.177 mole) sodium borohydride (finely powdered in a ball mill) and 100 ml. absolute dioxane. The mixture was cooled to room temperature and a solution of 9.6 gm. (0.03 mole) 4,4,6,8,8-pentanitro-l,ll-undecanedioyl chloride in 40 ml. dioxane was added over a period of about 15 minutes. After stirring for 4 hours a solution of 1.0 ml. acetic acid in 5 ml. dioxane was added slowly This produced an evolu tion of gas and slight warming; After stirring for 15 hours more, 1.5 ml. acetic acid in 6 ml. dioxane were added. This again produced slight Warming and considerable gas evolution. After stirring'for 4 hours longer, 1 ml. acetic acid in 6 ml. dioxane were added. The mixture had now become much more yellow.

Aftera totalof 26 hours, the mixture was hydrolyzed with icewater, and 26 ml. cone. hydrochloric-acid. -The product was recovered by extraction with ether and benzene, and crystallized from methylene chloride to destruction of functional groups, such as aliphatic nitro 7 groups, usually accompanies the reduction of the carbonyl group. This method is further complicated by the sensitivityof nitro groups t'o basic media, hence these reducing agents, although capable of effecting the reduction,

nevertheless have many undesirable features making it advantageous to find some more convenient method;

Wehave now found that polynitro diols can be prepared from their corresponding diacyl halides byreduction with sodium borohydride in accordance with the general re action scheme set forth below:

yield 3.5 gm. (43%) solid material, melting point 108 109 C. A sample was recrystallized for analysis from aqueous ethanol; The elemental analysis of the productis as follows:

Calculated: Percent C, 31.96; percent H, 4.63; percent N, 16.95. Found: Percent C, 32.46; percent H, 4.60; percent N, l6.90.

EXAMPLE l1 Bulk preparation of 4,4,6,8,8-pemanitr0"1,1I-

undecanedial .A reactor was charged. with 35 ordinary glass marbles, gm. finely powdered sodium borohydride and 2 liters. absolute dioxane. I With stirring, 1500 ml'. dioxane was removed by distillation, at which time the distillate was no longer basic. After cooling. to room temperature, a solution 1.5 ml. glacial aceticacid in 15ml. dioxane was added dropwise. While keeping the internal temperature af22-26 C., asolution of 1.45 gm. (0.303 mole) 4,4,6,8,8

dinitro-l,1l-undecanedioyl chloride in 600 m1. dioxane was added dropwise over a period of-about two hours. The mixture became veryviscous and 300 ml. dioxane was added at the mid-point. The cream-colored mixture gradually became thinner over a period of time. After a total of 7 hours, the mixture was cautiously poured into a stirred mixture of 400 ml. cone. hydrochloric acid and excess ice. The final mixture had a volume of about 8 liters. During the hydrolysis a grey oil was isolated by filtration and the aqueous dioxane filtrate was extracted with ether and benzene and crystallized from methylene chloride. absolute ethanol, benzene and cyclohexane and treated ,with decolorizing carbon. The solution was cooled and EXAMPLE 1H Preparation of 4,4,6,8,8-hexanitr-1,II-undecanedlol By following the procedure described in detail in The product was dissolved in a mixture of Example II and allowing the reaction to proceed for 7 I hours, 4,4,6,6,8,8,-hexanitro-1,ll-undecanedioyl chloride was reduced to produce 4,4,6,6,8,8-hexanitro-1,1l-undecanediol in a yield. The product has a melting point of 125-125.5 C. and a heat of combustion of 3222 cal/gram. The elemental analysis of the product is as follows:

Calculated: Percent C, 28.84; percent H, 3.94; percent N, 18.34. Found: Percent C, 29.50; percent H,- 3.84; percent N, 18.49. I The 4,4,6,6,8,8-hexanitro-l,1l-undecylene glycol diacetate derivative was prepared by treating the product with acetyl chloride in the conventional manner. The derivative had a melting point of 77.5-78.5 C. and the following analysis:

Calculated: Percent C, 33.21; percent H, 4.09; percent N, 15.50. Found: Percent C, 33.51; percent I-I,.4.29; percent N, 15.87.

The polynitro diacyl halides used as starting materials in the practice of our invention are prepared from their corresponding acids by conventional means. The acids, for example, 4,4,6,6,8,8-hexanitro-1,1l-undecanedioic acid, are prepared by hydrolysis of their corresponding esters which are prepared by the addition of a nitro-containing ester, having a labile hydrogen radical, to an unsaturated nitro-containing ester in accordance with the method disclosed in assignees copending application Ser. No.-337,2ll, filed February 16, 1953, now abandoned.

It is apparent that by merely selecting an appropriate polynitro substituted diacyl halide any member of this I a 4 We claim: 1. As compositions of matter the polynitro diols having the formula:

wherein A and A are lower alkylene radicals and Ris a radicalselected from the'group consisting of hydrogen and nitro radicals.

2. As compositions of matter the polynitro diols having theformula: l

. a so, No, No, no onr-a -o-oHr-on cE,-o-A'-cn,--on: 5 no, no.

wherein and'Aafe' lower alkylene radicals.

3. As compositions of matter the polynitro diols having the formula:

wherein A and A are lower alkylene radicals.

4. As compositions of matter 4,4,6,8,8-pentanitro-I,1l

undecanediol having the structural formula:

No, N0, No, K

. a i No, No, No, no-ontonicm-e-cnr- -cn.-e-omcn=on{-oi:

N0: N0: N0:

6. As a composition of matter 3,3,5,5,7,7-hexanitro-l,9 nonanediol having the structural formula: T

No, No. No, no-on,on,-c :on,- -oE,-e-on,on,-oH-; N0: NO: NO: .Q

' 7. The method of preparing polynitro diols having the formula: I I

N0: N0: N0: -no-on+-A-c-oH.-' -cHro-.A '-cH.-on 111 05 NO: 7

new class of polynitro diols can be prepared by reducing which comprises reducing a polynitro diacyl halide hav ing the formula: V No, No, No, '0 II A ll xa-o-a- -onr- -onr- -A'-o-x NO: N02

with sodium borohydride wherein A and A are lower alkylene radicals, R is a radical selected from the group consisting of hydrogen and nitro radicals, and X is a i halogen radical.

our invention to utilizepolynitro acid chlorides as start-j r materials for reasons of cost and convenience, however,it should be understood that any of the acid halides can be used. It will also be appreciated that reaction temperatures are not critical in the practice of our invention, and that bothhigher and lower temperatures and I 1 Conditions can be used if desired Without alfecting the course of the reaction. 1.

8. The method of claim'7 wherein the reactionis conducted in thepresence of an inert organic solvent.

9. The method of claim 7 wherein the reaction is conducted in the presence of 1,4-dioxane': IN

10. The method of preparing 4,4,6,8,8-pentanitrol,llundecanediol which comprises reducing 4,4,6,8,8-pentanitro-1,11-undecanedioyl chloride with sodium borohydride.

11. The method of preparing 4,4,6,6,8,8-hexanitro- 1,11-undecanediol which'comprises reducing 4,4,6,6,8,8-

' hexanitro-l,ll-undecanedioyl chloride with sodium borohydride.

5 12. The method of preparing 3,3,5,5,7,7-hexanitr0-1,9- nonanediol which comprises reducing 3,3,5,5,7,7-hexanitro-1,9-nonanedioyl chloride with sodium borohydride.

UNITED STATES PATENTS References Cited in the file of this patent 2,522,959 Plant Sept. 19, 1950 6 Plant Mar. 6, 1951 Plant Nov. 4, 1952 OTHER REFERENCES 

1. AS COMPOSITIONS OF MATTER THE POLYNITRO DIOLS HAVING THE FORNULA: 